Functionalized polyamines for clay mitigation

ABSTRACT

The present invention provides methods and compositions for treating clay-bearing aggregates, particularly those used for construction purposes, whereby inclusion of fines is maximized due to minimization of clay washing which tends to remove such fines, and whereby performance of the aggregate-containing construction material is enhanced. Exemplary methods comprise introducing to clay a water-soluble, functionalized polyamine comprising a water-soluble polyamine formed by reacting an amine compound with an epoxy compound, the polyamine thus reacted being functionalized through the use of certain halide, sulfate, or epoxy compounds.

This application is a divisional of U.S. patent application Ser. No.14/378,158 with a 371 filing date of Oct. 6, 2014, which is a 371 of PCTInternational Application No. PCT/EP2012/058830 filed May 11, 2012,which claims priority of U.S. Provisional Application Ser. No.61/601,730 filed Feb. 22, 2012.

FIELD OF THE INVENTION

This invention relates to the treatment of sand aggregates used formaking construction materials, and more particularly to the mitigationof clay in construction aggregates using a functionalized polyamine aswill be further described in detail.

BACKGROUND OF THE INVENTION

Clay materials are often present in construction materials such asconcrete, mortar, asphalt, road base, and gas and oil well drilling mud(used for cementing the annulus gap between pipe and well bore) due totheir presence in sand, crushed rock or gravel, and other aggregatematerials which are typically used in construction applications. Havinga lamellar structure, clay can absorb water and chemical agents,resulting in decreased performance of the construction materials. Acommon method to mitigate the deleterious effect of clays is to washthem from the aggregates. However, beneficial fines can also be removedduring washing.

It is known to use quaternary amine compounds for modifying propertiesor characteristics of clays. For example, in U.S. Pat. Nos. 6,352,952and 6,670,415 (owned by W. R. Grace & Co. Conn.), Jardine et al.disclosed that quaternary amines could be used to minimize the adverseeffect of clays on dosage efficiency of superplasticizers used inconcretes manufactured using sand aggregates that contained such clays.

As another example, in U.S. patent application Ser. No. 11/575,612(Publ. No. 2007/0287794 A1) and U.S. patent application Ser. No.11/575,607 (Publ. No. 2008/0060556 A1), assigned to Lafarge S. A.,Jacquet et al. disclosed compositions for “inerting” clays in aggregateswhich included quaternary amine functional groups, such asdiallyldialkyl ammonium, quaternized (meth)acrylates ofdialkylaminoalkyl and (meth)acrylamides N-substituted by a quaternizeddialkylaminoalkyl. Included among these groups were cationic polymersobtained by polycondensation of dimethylamine and epichlorohydrin.Similar compositions were disclosed by Brocas in World IntellectualProperty Organization Application (Publ. No. 2010/112784 A1), alsoassigned to Lafarge S. A.

This invention is related to a method and composition using afunctionalized polyamine for mitigating detrimental effects of clayswhile leaving beneficial fines. One objective of the present invention,therefore, is to mitigate the deleterious effects of clays whileimproving properties of the construction materials. Advantages of thisinvention include the improvement of mortar and concrete properties(e.g., workability, strength), asphalt properties (e.g., binder demand),and road base properties (e.g., improved flowability). As a result,washing can be reduced or eliminated, and this allows for a greatercontent of beneficial fines (i.e., small aggregates) to remain in theconstruction material.

Additional benefits can also be realized for clay stabilization in gasand oil well applications (involving fractured rock formations) toreduce water loss.

SUMMARY OF THE INVENTION

The present invention relates to clay-mitigation methods andcompositions which are believed to be useful in modifying clays that arecarried or otherwise mixed within inorganic particulates such as sandaggregates, crushed stone (gravel, rocks, etc.), granulated slag, andother inorganic particulate materials useful in construction materials.

The clay-mitigation agents of the present invention may be incorporatedinto clay-bearing construction aggregates and materials, such as mortar,concrete, asphalt, road base, or well bore drilling fluids and muds. Theclay mitigation agents may be introduced into dry or wet aggregates.

In the case of hydratable cementitious compositions, the clay-mitigationmethods and compositions of the present invention can provide improvedworkability without increasing water demand; and, in the case oftreating or washing aggregate materials, the inventive compositions canreduce the effort required for washing and/or disposing of claycontained in the aggregates.

An exemplary method of the present invention for mitigating claycomprises: introducing to clay contained in aggregates (e.g., mortar orconcrete aggregates, asphalt aggregates, road base aggregates), in anamount of 0.1% to 100% by weight based on dry weight of the claycontained in said aggregates, a water-soluble functionalized polyaminecomprising a water-soluble polyamine formed by reacting at least one ofthe amine compounds represented by the structural formulae (A) through(C) below with an epoxy compound represented by the structural formula(D) below:

wherein R¹ to R¹² each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine, bromine, iodine atom, or mixture thereof;and the molar ratio of hydrogen bonded to nitrogen of said aminecompound to the epoxy group of said epoxy compound is from 50:50 to75:25;

wherein said water-soluble polyamine is being functionalized using atleast one functionalizing agent selected from the following compounds:halide compounds represented by structural formulae (E) and (F) below;sulfate compounds represented by structural formula (G) below; epoxycompounds represented by structural formula (H) below; and dihalidecompounds represented by formula (I) below

wherein R¹³ to R¹⁶ each independently represent an aliphatic oraromatic, saturated or unsaturated, C₁ to C₁₆ alkyl group; R¹⁷represents a hydrogen, C₁ to C₅ alkyl, hydroxyalkyl, alkylene or arylgroup; R¹⁸ represents a C₁ to C₃ alkyl group; R¹⁹ represents a linear,branched or cyclic, C₁ to C₁₀ alkylene or arylene group, “X” representsa chlorine, bromine, iodine atom, or mixtures thereof; “Y⁻” represents achloride, bromide, or iodide anion; and “p” represents an integer of 1to 16; and

wherein the dry weight ratio of said polyamine to said functionalizingagent is from 99.5:0.5 to 75:25.

The present invention also provides admixture compositions containingthe above-described functionalized polyamine for treating clay-bearingaggregates in combination with at least one chemical admixtureconventionally used for modifying hydratable mortar or concrete, such asone or more water reducing admixtures (e.g., a polycarboxylate combpolymer superplasticizer), or other conventional admixture oradmixtures, as will be further described in detail hereinafter.

Exemplary admixture compositions of the invention may be introduced toclay-bearing aggregates at or after the quarry or processing at anaggregates mine, or at the concrete mix plant, where the aggregates arecombined with cement to provide mortar or concrete compositions. Theymay also be introduced into crushed stone or rock which is contaminatedwith clay, such as crushed gravel or rocks from quarries which areprepared for road base or other construction use (e.g., foundations),and other construction applications.

The above-described water-soluble functionalized polyamine can also beused, in other construction methods, such as in wellbore drillingapplications, such as servicing wellbores using a wellbore servicingfluid, e.g., wellbore drilling (mud) fluid, mud displacement fluid,and/or wellbore cementing composition, to inhibit the swelling ofargillaceous (shale or clay) containing subterranean formationpenetrated by the wellbore, as hereinafter described in further detail.

Further advantages and benefits of the invention are described infurther detail hereinafter.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to methods and compositions for treatingclays contained in aggregates such as sand, crushed rock, crushedgravel, drilling mud, and other clay-bearing aggregates, which are usedin or as part of construction materials. Exemplary compositions of theinvention include aggregate compositions, road base, and asphalts, aswell as cementitious compositions containing aggregates, such as mortarsand concretes.

The present invention relates to treatment of all types of clays. Theclays may include but are not limited to swelling clays of the 2:1 type(such as smectite type clays) or also of type 1:1 (such as kaolinite) orof the 2:1:1 type (such as chlorite). The term “clays” has referred toaluminum and/or magnesium silicates, including phyllosilicates having alamellar structure; but the term “clay” as used herein may also refer toclays not having such structures, such as amorphous clays. The presentinvention is also not limited to clays which absorb polyoxyalkylenesuperplasticizers (such as ones containing ethylene oxide (“EO”) and/orpropylene oxide (“PO”) groups), but it also includes clays that directlyaffect the properties of construction materials, whether in their wet orhardened state. Clays which are commonly found in sands include, forexample, montmorillonite, illite, kaolinite, muscovite, and chlorite.These are also included in the methods and compositions of the presentinvention.

Clay-bearing sands and/or crushed rock or gravel which are treated bythe method of the present invention may be used in cementitiousmaterials, whether hydratable or not, and such cementitious materialsinclude mortar, concrete, and asphalt, which may be used in structuralbuilding and construction applications, roadways, foundations, civilengineering applications, as well as in precast and prefabricationapplications.

The term “sand” as used herein shall mean and refer to aggregateparticles usually used for construction materials such as concrete,mortar, and asphalt, and this typically involves granular particles ofaverage size between 0 and 8 mm (e.g., not including zero), and, morepreferably, between 2 and 6 mm. Sand aggregates may comprisecalciferous, siliceous or siliceous limestone minerals. Such sands maybe natural sand (e.g., derived from glacial, alluvial, or marinedeposits which are typically weathered such that the particles havesmooth surfaces) or may be of the “manufactured” type, which are madeusing mechanical crushers or grinding devices.

The term “cement” as used herein includes hydratable cement and Portlandcement which is produced by pulverizing clinker consisting of hydrauliccalcium silicates and one or more forms of calcium sulfate (e.g.,gypsum) as an interground additive. Typically, Portland cement iscombined with one or more supplemental cementitious materials, such asPortland cement, fly ash, granulated blast furnace slag, limestone,natural pozzolans, or mixtures thereof, and provided as a blend. Theterm “cementitious” refers to materials that comprise Portland cement orwhich otherwise function as a binder to hold together fine aggregates(e.g., sand), coarse aggregates (e.g., crushed stone, rock, gravel), ormixtures thereof.

The term “hydratable” is intended to refer to cement or cementitiousmaterials that are hardened by chemical interaction with water. Portlandcement clinker is a partially fused mass primarily composed ofhydratable calcium silicates. The calcium silicates are essentially amixture of tricalcium silicate (3CaO.SiO₂, “C₃S” in cement chemistsnotation) and dicalcium silicate (2CaO.SiO₂, “C₂S”) in which the formeris the dominant form, with lesser amounts of tricalcium aluminate(3CaO.Al₂O₃, “C₃A”) and tetracalcium aluminoferrite (4CaO.Al₂O₃.Fe₂O₃,“C₄AF”). See e.g., Dodson, Vance H., Concrete Admixtures (Van NostrandReinhold, New York N.Y. 1990), page 1.

The term “concrete” will be used herein generally to refer to ahydratable cementitious mixture comprising water, cement, sand, usuallya coarse aggregate such as crushed stone, rock, or gravel, and optionalchemical admixture(s).

It is contemplated that one or more conventional chemical admixtures maybe used in the methods and compositions of the present invention. Theseinclude, without limitation, water reducing agents (such as ligninsulfonate, naphthalene sulfonate formaldehyde condensate (NSFC),melamine sulfonate formaldehyde condensate (MSFC), polycarboxylate combpolymers (containing alkylene oxide groups such as “EO” and/or “PO”groups), gluconate, and the like); set retarders; set accelerators;defoamers; air entraining agents; surface active agents; and mixturesthereof.

Of the admixtures, the EO-PO type polymers, which have ethylene oxide(“EO”) and/or propylene oxide (“PO”) groups and polycarboxylate groups,are preferred. Cement dispersants contemplated for use in methods andcompositions of the invention include EO-PO polymers and EO-PO combpolymers, as described for example in U.S. Pat. Nos. 6,352,952 B1 and6,670,415 B2 of Jardine et al., which mentioned the polymers taught inU.S. Pat. No. 5,393,343 (assigned to W. R. Grace & Co. Conn.). Thesepolymers are available from Grace Construction Products, Massachusetts,USA, under the trade name ADVA®. Another exemplary cement dispersantpolymer, also containing EO/PO groups, is obtained by polymerization ofmaleic anhydride and an ethylenically-polymerizable polyalkylene, astaught in U.S. Pat. No. 4,471,100. In addition, EO/PO-group-containingcement dispersant polymers are taught in U.S. Pat. Nos. 5,661,206 and6,569,234. The amount of such polycarboxylate cement dispersants usedwithin concrete may be in accordance with conventional use (e.g., 0.05%to 0.25% based on weight of active polymer to weight of cementitiousmaterial).

Thus, exemplary admixture compositions of the invention comprise atleast one chemical admixture, such as one or more polycarboxylate cementdispersants, which is/are preferably polycarboxylate comb polymer(s)having EO and/or PO groups, in combination with the water-solublefunctionalized polyamine, as described herein.

As mentioned in the summary, an exemplary method of the presentinvention for mitigating the effects of clay in aggregates comprises:introducing to clay contained in aggregates (e.g., mortar or concreteaggregates, asphalt aggregates, road base aggregates), in an amount of0.1% to 100% by weight based on dry weight of the clay contained in saidaggregates, a water-soluble functionalized polyamine comprising awater-soluble polyamine formed by reacting at least one of the aminecompounds represented by the structural formulae (A) through (C) belowwith an epoxy compound represented by the structural formula (D) below:

wherein R¹ to R¹² each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine, bromine, iodine atom, or mixture thereof;and the molar ratio of hydrogen bonded to nitrogen of said aminecompound to the epoxy group of said epoxy compound is from 50:50 to75:25;

wherein said water-soluble polyamine is being functionalized using atleast one functionalizing agent selected from the following compounds:halide compounds represented by structural formulae (E) and (F) below;sulfate compounds represented by structural formula (G) below; epoxycompounds represented by structural formula (H) below; and dihalidecompounds represented by formula (I) below

wherein R¹³ to R¹⁶ each independently represent an aliphatic oraromatic, saturated or unsaturated, C₁ to C₁₆ alkyl group; R¹⁷represents a hydrogen, C₁ to C₅ alkyl, hydroxyalkyl, alkylene or arylgroup; R¹⁸ represents a C₁ to C₃ alkyl group; R¹⁹ represents a linear,branched or cyclic, C₁ to C₁₀ alkylene or arylene group, “X” representsa chlorine, bromine, iodine atom, or mixtures thereof; “Y⁻” represents achloride, bromide, or iodide anion; and “p” represents an integer of 1to 16; and

wherein the dry weight ratio of said polyamine to said functionalizingagent is from 99.5:0.5 to 75:25.

The term “functionalized,” as used herein refers to the chemicalreaction of one or more functionalizing agents (or a mixture thereof)with the non-quaternized amine groups of the polyamine. Depending on thestructure of the polyamine precursor, the term “functionalized” may meanquaternized, coupled, alkylated, etc. Based on the dry weight ratio ofsaid polyamine to said functionalizing agent, their respective chemicalstructure and the yield of the chemical reaction, the conversion rate ofthe amines of said polyamine to functionalized amines may be partial ortotal. In another embodiment, the functionalizing agent can be added inmolar excess to ensure total conversion of the amines groups and willremain in excess in the functionalized resulting polyamine.

Thus, in further exemplary embodiments of the present invention, thewater-soluble polyamine, formed by combining at least one of compounds Athrough C with D, may be used in a mixture with a water-soluble compoundselected from the “functionalizing agents” as identified in structuralformulae E through I (e.g., without having to undergo a chemicalreaction). Accordingly, methods of the invention for treatingaggregates, admixture compositions of the invention, and cementitiouscompositions of the invention may comprise a mixture of thewater-soluble polyamine and at least one water-soluble compound selectedfrom compounds identified by structural formulae E through I. Suchexemplary mixtures would include one or more water-soluble compoundsselected from among those represented by structural formulae E throughI.

A process for making cationic polyamines functionalized with analkylating agent is described in WO 2009/127893 A1 of Favero et al. (Seee.g., at page 4, identifying epichlorohydrin-dimethylamine as example ofpolyamine that can be functionalized with at least one alkylatingagent).

According to the present invention, water-soluble functionalizedpolyamine are introduced to clay contained in aggregates (e.g., mortaror concrete aggregates, asphalt aggregates, road base aggregates), inthe amount of 0.1 to 100% (as previously mentioned), more preferably inan amount of 1% to 50%, and most preferably in an amount of 2% to 25% byweight based on dry weight of the clay contained in said aggregates.

Thus, the first phase of making the functionalized polyamines of thepresent invention is first to form the water-soluble polyamine byreacting one or more amines represented by formulae A, B, and/or C (orany or all of these in combination) with an epoxy compound (representedby formula D), such as epichlorohydrin, epibromohydrin, epiiodohydrin,or a mixture thereof. Preferred among the epoxy compounds isepichlorohydrin.

In further exemplary embodiments, the water-soluble polyamine comprisesan amine represented by structural formula (A), and comprises anammonia, methylamine, ethylamine, propylamine, dimethylamine,diethylamine, dipropylamine, methyl ethyl amine, methyl propyl amine,ethyl propyl amine, or mixture thereof. Preferred is dimethylamine.

In still further exemplary embodiments, the water-soluble polyaminecomprises an amine represented by structural formula (B), and comprisesethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine,1,5-pentamethylene diamine, 1,6-hexamethylene diamine, or mixturethereof. Preferred is ethylene diamine, hexamethylene diamine, ormixture thereof.

In still further exemplary embodiments, the water-soluble polyaminecomprises an amine represented by structural formula (C), and comprisesdiethylene triamine, triethylene tetramine, tetraethylene pentamine, ormixture thereof. Preferred is tetraethylene pentamine.

As previously mentioned, the water-soluble polyamine may comprisemixtures of amines represented by formulae A, B, and C. For example, anyor all of dimethylamine (formula A) and ethylene diamine (formula (B)and/or tetraethylene pentamine (formula C) can be combined with one ormore epoxy compounds as represented by formula D. For example, the molarratio of an amine from formula A with an amine from formula B and/or Ccan be provided in a molar ratio of 99.9:0.1 to 90:10. Any combinationof an amine represented by formulae B and/or C should preferably notconstitute more than 10 molar percent.

In the second phase of making functionalized polyamines of the presentinvention, the water-soluble polyamine is functionalized using at leastone functionalizing agent selected from the following compounds: halidecompounds represented by structural formulae (E) and (F); sulfatecompounds represented by structural formula (G); epoxy compoundsrepresented by structural formula (H); and dihalide compoundsrepresented by formula (I). Two or more of these compound groups may beemployed.

In exemplary functionalized water-soluble polyamines, thefunctionalization of the polyamine is accomplished using a halidecompound represented by structural formula (E), the halide compound maybe selected from methyl chloride, ethyl chloride, propyl chloride, allylchloride, benzyl chloride, or mixtures thereof. Preferred among thesehalide compounds are methyl chloride, benzyl chloride, or mixturesthereof.

In other preferred embodiments, the water-soluble polyamine isfunctionalized using a halide compound represented by structural formula(F), said sulfate compound comprising 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyl dimethyllaurylammonium chloride, 3-chloro-2-hydroxypropyl dimethylstearylammonium chloride, 3-chloro-2-hydroxypropyl dimethylcocoalkylammonium chloride, or mixtures thereof. Preferred among thesehalide compounds is 3-chloro-2-hydroxypropyl trimethylammonium chloride.

In other exemplary embodiments, the water-soluble polyamine isfunctionalized using a sulfate compound represented by structuralformula (G), the halide compound comprising dimethyl sulfate, diethylsulfate, methyl ethyl sulfate, methyl propyl sulfate, or mixturesthereof. Preferred among these is dimethyl sulfate.

In other exemplary embodiments, the water-soluble polyamine isfunctionalized using an epoxy compound represented by structural formula(H), the epoxy compound comprising glycidyl trimethylammonium chloride,glycidyl triethylammonium chloride, glycidyl dimethyl propylammoniumchloride, glycidyl dimethylhexylammonium chloride, glycidyldipropyldecylammonium bromide, glycidyl dimethyl laurylammoniumchloride, or mixtures thereof. Preferred among these epoxy compounds isglycidyl trimethylammonium chloride.

In other exemplary embodiments, the water-soluble polyamine isfunctionalized using a dihalide compound represented by structuralformula (I), the dihalide compound comprising dichloroethane,dichloropropane, dichlorobutane, dibromoethane, dibromopropane,dibromobutane, dichlorobenzene, dibromobenzene, 1-bromo-4-chlorobenzene,or mixtures thereof. Preferred among these are dichloroethane anddiromobutane.

In preferred embodiments, the weight ratio of the water-solublepolyamine to functionalizing agent is 99:1 to 85:15; and, morepreferably, 99:1 to 90:10.

The water-soluble functionalized polyamine has a Brookfield viscosity of2 to 500 centipoise (hereinafter “cP”) at 50 wt % aqueous solution whenmeasured at 60 rpm and 25° C. using Brookfield viscometer model DV-II+,spindle LV-1. More preferably, the polymer has a Brookfield viscosity of4 to 200 cP at 50 wt % aqueous solution.

The water-soluble functionalized polyamine also preferably has aweight-average molecular weight of 2,000 to 100,000, and more preferably5,000 to 50,000, as measured by aqueous gel permeation chromatography(GPC) with refractive index detection using poly(ethylene glycol) asstandard. The GPC conditions are as follows: two TSK-gel PWXL-CO columns(G3000 and G5000), column temperature at 35° C., 0.8 wt % aqueoussolution of sodium nitrate as elution solvent, injection volume of 50μL, and flow rate of 0.6 mL/min.

The present invention also provides an aggregate composition comprisinga plurality of clay-bearing aggregates selected from the group ofnatural and/or manufactured sand, crushed stone, crushed gravel, crushedrock, crushed shale, or mixtures thereof; and, in an amount of 0.1% to100% by weight based on dry weight of the clay contained in saidaggregates, a water-soluble functionalized polyamine comprising awater-soluble polyamine formed by reacting at least one of the aminecompounds represented by the structural formulae (A) through (C) belowwith an epoxy compound represented by the structural formula (D) below:

wherein R¹ to R¹² each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine, bromine, iodine atom, or mixture thereof;and the molar ratio of hydrogen bonded to nitrogen of said aminecompound to the epoxy group of said epoxy compound is from 50:50 to75:25;

wherein said water-soluble polyamine is being functionalized using atleast one functionalizing agent selected from the following compounds:halide compounds represented by structural formulae (E) and (F) below;sulfate compounds represented by structural formula (G) below; epoxycompounds represented by structural formula (H) below; and dihalidecompounds represented by formula (I) below

wherein R¹³ to R¹⁶ each independently represent an aliphatic oraromatic, saturated or unsaturated, C₁ to C₁₆ alkyl group; R¹⁷represents a hydrogen, C₁ to C₅ alkyl, hydroxyalkyl, alkylene or arylgroup; R¹⁸ represents a C₁ to C₃ alkyl group; R¹⁹ represents a linear,branched or cyclic, C₁ to C₁₀ alkylene or arylene group, “X” representsa chlorine, bromine, iodine atom, or mixtures thereof; “Y⁻” represents achloride, bromide, or iodide anion; and “p” represents an integer of 1to 16; and

wherein the dry weight ratio of said polyamine to said functionalizingagent is from 99.5:0.5 to 75:25.

In further exemplary embodiments, the water-soluble functionalizedpolyamine is introduced to clay contained in aggregates (e.g., mortar orconcrete aggregates, asphalt aggregates, road base aggregates), in anamount of 0.1-100%, more preferably 1% to 50%, and, most preferably, 2%to 25%, all percentages based on dry weight of clay contained in or onthe aggregates.

It is understood that the foregoing description of an aggregatecomposition applies to a clay-bearing plurality of aggregates which maybe in a dry pile state (e.g., located in supply piles at the mine orquarry or concrete plant; located at a preparation site for installationas road base) or may be within a wet cementitious slurry (e.g.,concrete, mortar). With respect to dry aggregate compositions of thepresent invention containing said water-soluble functionalized polyamine(which is deposited upon or mixed into the aggregates), an exemplarymethod of the present invention for modifying cementitious compositionscomprises combining the dry aggregate containing said water-solublefunctionalized polyamine with a hydratable cement.

The present invention also provides an admixture composition fortreating compositions containing clay-bearing aggregates (e.g.,hydratable cementitious compositions, dry or wet aggregate piles,asphalt, etc.) comprising:

at least one chemical admixture selected from the group of waterreducing agents (e.g., lignin sulfonate, naphthalene sulfonateformaldehyde condensate (NSFC), melamine sulfonate formaldehydecondensate (MSFC), polycarboxylate comb polymers (containing alkyleneoxide groups such as “EO” and/or “PO” groups), gluconate, and the like);set retarders; set accelerators; defoamers; air entraining agents;surface active agents; and mixtures thereof; and

a water-soluble functionalized polyamine comprising a water-solublepolyamine formed by reacting at least one of the amine compoundsrepresented by the structural formulae (A) through (C) below with anepoxy compound represented by the structural formula (D) below:

wherein R¹ to R¹² each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine, bromine, iodine atom, or mixture thereof;and the molar ratio of hydrogen bonded to nitrogen of said aminecompound to the epoxy group of said epoxy compound is from 50:50 to75:25;

wherein said water-soluble polyamine is being functionalized using atleast one functionalizing agent selected from the following compounds:halide compounds represented by structural formulae (E) and (F) below;sulfate compounds represented by structural formula (G) below; epoxycompounds represented by structural formula (H) below; and dihalidecompounds represented by formula (I) below

wherein R¹³ to R¹⁶ each independently represent an aliphatic oraromatic, saturated or unsaturated, C₁ to C₁₆ alkyl group; R¹⁷represents a hydrogen, C₁ to C₅ alkyl, hydroxyalkyl, alkylene or arylgroup; R¹⁸ represents a C₁ to C₃ alkyl group; R¹⁹ represents a linear,branched or cyclic, C₁ to C₁₀ alkylene or arylene group, “X” representsa chlorine, bromine, iodine atom, or mixtures thereof; “Y⁻” represents achloride, bromide, or iodide anion; and “p” represents an integer of 1to 16; and

wherein the dry weight ratio of said polyamine to said functionalizingagent is from 99.5:0.5 to 75:25.

In further exemplary embodiments, the admixture compositions comprise atleast one chemical admixture selected from the group ofoxyalkylene-containing water-reducing admixture, shrinkage reducingadmixture, or mixture thereof, in combination with said water-solublefunctionalized polyamine. Exemplary methods of the invention comprisecombining said admixture compositions with a hydratable cementitiousbinder, either before, during, or after combining said cementitiousbinder with clay-bearing aggregates to create a mortar or concretematerial.

For construction materials generally, the functionalized water-solublepolyamines of the present invention may be introduced to aggregates(e.g., sand) by application to the clay-bearing aggregates at the quarryor mine; by application at the concrete mix plant where the aggregatesare combined with cement to form hydratable mortar or concrete; or byapplication at an asphalt plant wherein clay-bearing aggregates arecombined with bituminous binder. The polymer may also be incorporatedinto the aggregates at the concrete mix plant before the cement binderis added or into dry or wet mortar or concrete containing theaggregates. Additionally, the polymer may be used together withconventional concrete admixtures such as water reducers, retarders,accelerators, superplasticizers, air detraining agents, air entrainingagent, and the like.

Concerning gas and oil well applications, the functionalizedwater-soluble polyamines of the present invention may be introduced intothe aqueous well bore cement slurry or drilling fluid or mud, which inturn stabilizes subterranean clay-bearing formations.

As mentioned in the summary, the above-described water-solublefunctionalized polyamine can also be used in wellbore drillingapplications, such as wellbore mud drilling fluid and/or wellborecementing compositions and methods for servicing wellbores. As describedin US 2007/0261849 of Valenziano et al., natural resources such as gas,oil, and water residing in subterranean formations or zones are usuallyrecovered by drilling a wellbore down to the subterranean formationwhile circulating a drilling fluid (also known as a drilling mud)through the drill pipe and the drill bit and upwardly through thewellbore to the surface. The drilling fluid serves to lubricate thedrill bit and carry drill cuttings back to the surface. After thewellbore is drilled to the desired depth, the drill pipe and drill bitare typically withdrawn from the wellbore while the drilling fluid isleft in the wellbore while the drilling fluid is left in the wellbore toprovide hydrostatic pressure on the formation penetrated by the wellboreand thereby prevent formation fluids from flowing into the wellbore.Next, the wellbore drilling operation involves running a string of pipe,e.g., casing, in the wellbore. Primary cementing is then typicallyperformed whereby a cement slurry is pumped down through the string ofpipe and into the annulus between the string of pipe and the walls ofthe wellbore, whereby the drilling mud is displaced, and the cementslurry sets into a hardened mass (i.e., sheath) and thereby seals theannulus.

The present inventors believe that the above-described water-solublefunctionalized polyamine is suitable for use as a clay mitigating agentin aqueous wellbore drilling fluid (mud) compositions and/or wellborecementing compositions. Among the advantages or purposes of doing thisis to stabilize argillaceous formations like shales and/or clays in thewellbore which could otherwise be weakened and displaced by water in theaqueous wellbore mud. Because of the saturation and low permeability ofa shale formation, penetration of a small volume of wellbore fluid intothe formation can result in a considerable increase in pore fluidpressure near the wellbore wall, which, in turn, can reduce theeffective cement support, which leads to a less stable wellborecondition.

Thus, the present invention also concerns a method for servicing awellbore comprising: introducing to a wellbore formation an aqueouswellbore servicing fluid (e.g., drilling mud, spacer fluid, muddisplacement fluid, cementing composition, or combination thereof)comprising a water-soluble functionalized polyamine comprising awater-soluble polyamine formed by reacting at least one of the aminecompounds represented by the structural formulae (A) through (C) belowwith an epoxy compound represented by the structural formula (D) below:

wherein R¹ to R¹² each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine, bromine, iodine atom, or mixture thereof;and the molar ratio of hydrogen bonded to nitrogen of said aminecompound to the epoxy group of said epoxy compound is from 50:50 to75:25;

wherein said water-soluble polyamine is being functionalized using atleast one functionalizing agent selected from the following compounds:halide compounds represented by structural formulae (E) and (F) below;sulfate compounds represented by structural formula (G) below; epoxycompounds represented by structural formula (H) below; and dihalidecompounds represented by formula (I) below

wherein R¹³ to R¹⁶ each independently represent an aliphatic oraromatic, saturated or unsaturated, C₁ to C₁₆ alkyl group; R¹⁷represents a hydrogen, C₁ to C₅ alkyl, hydroxyalkyl, alkylene or arylgroup; R¹⁸ represents a C₁ to C₃ alkyl group; R¹⁹ represents a linear,branched or cyclic, C₁ to C₁₀ alkylene or arylene group, “X” representsa chlorine, bromine, iodine atom, or mixtures thereof; “Y⁻” represents achloride, bromide, or iodide anion; and “p” represents an integer of 1to 16; and

wherein the dry weight ratio of said polyamine to said functionalizingagent is from 99.5:0.5 to 75:25.

In addition to the water-soluble functionalized polyamine, the exemplarydrilling mud or cementing composition can further contain conventionalcementitious compositions, surfactants, or combinations thereof. Forexample, the cementitious composition may comprise a cement such as ahydraulic cement (as previously defined above), and this cement mayinclude calcium, aluminum, silicon, oxygen, and/or sulfur and which setsand hardens by reaction with water. Examples of hydraulic cementsinclude but are not limited to Portland cements (e.g., classes A, C, G,and H Portland cements), pozzolan cements, high alumina cements, silicacements, high alkalinity cements, and combinations thereof.

While the invention is described herein using a limited number ofembodiments, these specific embodiments are not intended to limit thescope of the invention as otherwise described and claimed herein.Modification and variations from the described embodiments exist. Morespecifically, the following examples are given as a specificillustration of embodiments of the claimed invention. It should beunderstood that the invention is not limited to the specific details setforth in the examples. All parts and percentages in the examples, aswell as in the remainder of the specification, are by percentage dryweight unless otherwise specified.

EXAMPLE 1

A 2 L flask equipped with a condenser, a thermometer, a mechanicalstirrer, and an addition funnel was charged with 60% aqueousdimethylamine (DMA, 432 g) and water (187 g). Into the flask, 456 g ofepichlorohydrin (EPI) was added slowly over 3 hours while maintainingthe temperature between 70°-80° C. An additional 24 g of epichlorohydrinwas charged over 2 hours at 80° C. The resulting condensate (“EPI-DMA”)was thereafter functionalized with a specific amount of 65% aqueoussolution of the functionalizing agent, namely 3-chloro-2-hydroxypropyltrimethylammonium chloride (“CHPTMAC”), by reacting them for 30 minutesat 80° C. Thereafter, water was added to obtain an aqueous solution.These amounts are reflected in Table 1.

The viscosity (in centipoise) of a 50% aqueous solution of the resultingpolymer was measured using Brookfield viscometer model DV-II+, spindleLV-1 at 60 rpm, 25° C. The weight-average molecular weight (Mw) andnumber-average molecular weight (Mn) were measured by aqueous gelpermeation chromatography (GPC) with refractive index detection usingpoly(ethylene glycol) as standard. The GPC conditions are as follows:two TSK-gel PWXL-CO columns (G3000 and G5000), column temperature at 35°C., 0.8 wt % aqueous solution of sodium nitrate as elution solvent,injection volume of 50 μL, and flow rate of 0.6 mL/min.

Using the above procedure, the following polymers were synthesized,designated as “CMA-#” (to indicate Clay Mitigation Agent sample withnumber), and summarized in Table 1.

TABLE 1 EPI-DMA CHPTMAC Description (g) (g) Viscosity (cP) Mw MnControl-1 100 0.0 8.4 8300 5300 CMA-1 100 1.05 8.1 8300 5400 CMA-2 1002.63 8.4 9000 5600 CMA-3 100 5.26 9.2 8800 5500

EXAMPLE 2

The performance of the functionalized polyamines was evaluated inconcrete using sand doped with clay and was compared to a control,non-functionalized EPI-DMA material.

The concrete mix design included the following components: Cement—445kg/m³ with an alkali equivalent of 0.49% and a free calcium oxidecontent of 1.39%; Sand—884 kg/m³; Clay—sodium montmorillinite, 1.149g/m³ (0.13% solids/sand); Stone—886 kg/m³; Water—190 kg/m³ for awater-to-cement ratio of 0.427; Polycarboxylate superplasticizerformulated with a defoamer—0.145 wt % solids/cement. The dosage for thefunctionalized and non-functionalized polyamines was 10 wt %solids/clay.

The mixing procedure was as follows: (1) mix sand, clay, ⅓ of mixingwater and clay mitigating agent (functionalized or non-functionalizedpolyamine) together for five minutes; (2) add stone and mix for oneminute; (3) add cement and remaining water and mix for 2 minutes; (4)add polycarboxylate superplasticizer and mix for 2 minutes; (5) stopmixer and rest for 3 minutes; (6) re-mix for 2 minutes. After mixing,the slump flow (diameter of the spread), air content, and the 1-, 7-,and 28-day compressive strength of the concrete were determined. Theresults are shown in Table 2.

TABLE 2 Clay Mitigating Slump Flow Air Compressive Strength (MPa) atAgent (mm) (%) 1 day 7 day 28 day Control-1 540 2.1 23 42 47 CMA-1 5502.2 24 43 48 CMA-2 590 2.2 23 42 48 CMA-3 580 2.2 23 42 48

As shown in Table 2, the functionalized polyamines of the inventionclearly exhibit clay mitigating effect as they provide an increase inslump-flow workability as compared to the control while maintaining thecompressive strength at all ages.

EXAMPLE 3

To further demonstrate the effectiveness of the invention, concretetests were performed to determine the dosage required to achieve equalworkability.

The mix design and protocol were identical to those of Example 2 exceptthat the dosages of clay mitigating agents were varied. The controlpolyamine was tested from 5% to 10% solids/clay while the functionalizedpolyamine CMA-2 was tested from 3% to 9% solids/clay. Dosages wereadjusted to achieve similar slump values. Table 3 presents three slumpranges along with the required dosages and the dosage reduction enabledby the functionalized polyamine of the invention.

TABLE 3 Slump Flow Required Dose (% of clay) of Dose Reduction (mm)Control-1 CMA-2 (%) 510-520 5.0 3.0 40 600-610 7.8 6.0 24 660-670 10.08.5 15The results in Table 3 clearly indicate that CMA-2 of the invention is15% to 40% more effective as a clay mitigating agent than the control interms of achieving similar slump flow in the concrete.

EXAMPLE 4

Using the synthetic procedure of Example 1 and benzyl chloride (BZC) asfunctionalizing agent, the following clay mitigating agents weresynthesized and shown in Table 4.

TABLE 4 Description EPI-DMA (g) BZC (g) Viscosity (cP) Mw Mn Control-2100 0.0 8.4 8300 5300 CMA-4 100 0.5 10.9 10400 6500 CMA-5 100 1.2 12.012300 7400 CMA-6 100 2.3 12.3 12200 7200

EXAMPLE 5

Using the concrete testing procedure of Example 2, polyaminesfunctionalized with benzyl chloride were evaluated and the test resultsare illustrated in Table 5.

TABLE 5 Clay Mitigating Slump Flow Compressive Strength (MPa) at Agent(mm) Air (%) 1 day 7 day 28 day Control-2 540 2.1 23 42 47 CMA-4 580 2.223 41 48 CMA-5 590 2.1 23 43 48 CMA-6 600 2.1 23 43 49As shown in Table 5, polyamines of the present invention functionalizedwith benzyl chloride provide evidence of higher slump flow performancecompared to the control, thus confirming clay mitigating effects.

EXAMPLE 6

The benefit to asphalt and road base construction aggregates wasevaluated through the determination of the plasticity index. Model soilscomprised of clay and sand were treated with both a functionalizedpolyamine and a non-functionalized polyamine and compared to anon-treated soil sample.

The model soil sample included the following components: ungroundsilica—150 g with 100% passing No. 40 sieve (425 microns); andclay—sodium montmorillinite, 50 g. The first sample was left untreated,while the second sample was treated with 5% solids/claynon-functionalized polyamine Control-1. Next, the third sample wastreated with 4 wt % solids/clay functionalized polyamine CMA-2. Finally,the fourth and fifth samples were treated with 10 wt % solids/clay ofboth the non-functionalized and functionalized polyamines respectively.

The plasticity index was determined following the British Standard1377:2. The plasticity index is calculated as the liquid limit minus theplastic limit. The liquid limit was determined using the conepenetrometer method while the plastic limit was determined using arolling device. A lower plasticity index is typically indicative ofimproved adhesion between the aggregate and binder for asphalt and lowersusceptibility to frost-heave in road base. The results are shown inTable 6.

TABLE 6 Clay Mitigating Dosage Plasticity index Agent (% solids/clay)(%) None 0 22 Control-1 5 11 CMA-1 4 11 Control-1 10 NP CMA-1 10 NPAs shown in Table 6, at a 20% reduced dosage, the functionalizedpolyamine exhibits the same plasticity performance as thenon-functionalized polyamine. Both chemicals show a clear improvementover the non-treated model soil. At 10 wt %, both treatments render thesoil non-plastic (NP).

EXAMPLE 7

To demonstrate the effectiveness of the invention in aqueous wellboredrilling fluid (mud) compositions and/or wellbore cementingcompositions, a filtration method was performed to determine the abilityof different clay solutions to absorb water. Three solutions weretested: one without any treatment, one treated with a non-functionalizedpolyamine and the last treated with a functionalized polyamine.

The clay solution included the following components: distilled water—400g; and clay—sodium montmorillinite, 8 g. The first sample was leftuntreated, while the second sample was treated with 10% solids/claynon-functionalized polyamine Control-1. Lastly, the third sample wastreated with 10 wt % solids/clay functionalized polyamine CMA-2.

The absorption capacity of the clay was determined by a filtrationmethod similar to one described in U.S. Pat. No. 5,099,923. For thetreated samples, the chemical is added to the water and mixed by anoverhead stirrer at 600 rpm for 5 minutes. Afterwards, the clay is addedand mixed for an additional 5 minutes. For the untreated sample, theclay was added to the water and mixed at 600 rpm for 5 minutes toprovide a clay slurry. This slurry is then filtered over a hardenedfilter paper equivalent to Whatman™ Filter Paper #50. A low pressurevacuum (9.7 psi) was applied and the time required to achieve varioustotal volumes of water passing the filter was recorded. The data wasplotted against (time)^(1/2) and a slope value was calculated for eachtrial in units of mL/(time)^(1/2). Larger slopes indicate enhancedswelling inhibition. The results are shown in Table 7.

TABLE 7 Clay Mitigating Dosage Agent (% solids/clay) Time to 75 mL (sec)Slope mL/(sec)^(1/2) None 0 1512 NA Control-1 10 105 10.7 CMA-1 10 3023.5As shown in Table 7, the functionalized polyamine exhibits improvedswelling inhibition over the non-functionalized polyamine. A slope forthe untreated slurry was not calculated because only one reading wastaken at 75 mL. The rate of filtration was noticeably slower asindicated by the time to 75 mL, so no further readings were taken.

The foregoing examples and embodiments were presented for illustrativepurposes only and not intended to limit the scope of the invention.

It is claimed:
 1. An admixture composition for modifying one or moreproperties of an aggregate or cementitious composition, comprising: atleast one chemical admixture selected from the group consisting of waterreducing agents, set retarders, set accelerators, defoamers, airentraining agents, surface active agents, and mixtures thereof; and awater-soluble functionalized polyamine comprising a water-solublepolyamine formed by reacting at least one of the amine compoundsrepresented by the structural formulae (A) through (C) below with anepoxy compound represented by the structural formula (D) below:

wherein R1 to R12 each independently represent hydrogen or a C₁ to C₃alkyl group; “m” and “n” each independently represent an integer of 1 to6; “X” represents chlorine; and the molar ratio of hydrogen bonded tonitrogen of said amine compound to the epoxy group of said epoxycompound is from 50:50 to 75:25; wherein said water-soluble polyamine isfunctionalized using 3-chloro-2-hydroxypropyl trimethylammonium chlorideas a functionalizing agent; and wherein the dry weight ratio of saidpolyamine to said functionalizing agent is from 99:1 to 85:15.
 2. Theadmixture of claim 1 wherein said at least one chemical admixture is awater reducer selected from the group consisting of lignin sulfonate,naphthalene sulfonate formaldehyde condensate, melamine sulfonateformaldehyde condensate, polycarboxylate comb polymers which contain analkylene oxide group, gluconate, and mixtures thereof.
 3. The admixtureof claim 1, wherein the dry weight ratio of said polyamine to saidfunctionalizing agent is from 99:1 to 90:10.